Agents for combating pests

ABSTRACT

The present invention relates to the use of the sulphenic acid amides of the general formula (I) ##STR1## in which X represents identical or different halogen atoms, Y 1  and Y 2  are identical or different and represent hydrogen, halogen, alkyl, alkoxy, halogenoalkyl or NO 2  and 
     Z represents halogen, --OH, --NHOH or the group --OR 1 , 
     in which 
     R 1  denotes optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aryl, aralkyl and heterocyclyl, or 
     Z represents the group ##STR2## in which R 2  and R 3  are identical or different and denote hydrogen or a heterocyclic radical, or 
     Z represents the group --OM 
     in which 
     M denotes ammonium or the equivalent of an alkali metal, alkaline earth metal or heavy metal cation, 
     for prolonging the duration of a high activity in agents for combating soil pests.

This is a division of U.S. application Ser. No. 798,216, filed Nov. 14, 1985, now U.S. Pat. No. 4,656,163, which in turn was a division of U.S. application Ser. No. 701,476, filed Feb. 14, 1985, now U.S. Pat. No. 4,603,214.

The present invention relates to new agents for combating pests which can preferably be used in plant protection for combating nematodes and arthropods, in particular insects. The new agents for combating pests contain at least one suitable active compound from the series comprising carbamates, P esters (phosphoric acid esters and phosphonic acid esters, including the ester-amides and the particular thiono, thiol and thiono-thiol derivatives) and pyrethroids, and at least one suitable sulphenic acid amide. The new agents for combating pests are distinguished by a particularly long-lasting activity when used as nematicides and soil insecticides.

The combating of nematodes and soil insects is gaining ever more importance in intensive cultivation of crop plants. Insects which continuously or at times, for example during certain development stages, live in or on the soil or close to the soil, for example on parts of plants, are designated soil insects (compare also B. Homeyer in Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel [Chemistry of the Plant Protection Agents and Agents for Combating Pests], published by R. Wegler, Volume 1, Springer-Verlag, Berlin 1970, pages 464 to 474). Such pests should preferably be combated preventively, so that an agent for combating soil pests must be applied early and must have a reliable and adequate activity for the maximum possible period. It is frequently advantageous for the agents for combating pests already to be applied during sowing, in order to simultaneously achieve protection of the seed and of the developing young plants.

Since the soil treatment agents currently available do not always reliably display an adequately long activity under adverse weather and/or soil conditions, it is an object of the invention to provide new agents for combating pests which allow long-lasting protection of the plants, even under adverse conditions.

It has now been found that agents for combating pests which contain at least one substance, which is active against nematodes and/or insects, especially soil insects, e.g., carbamates, P esters and pyrethroids, (called the "active compound" below) and at least one sulphenic acid amid of the general formula (I) ##STR3## in which X represents identical or different halogen atoms,

Y¹ and Y² are identical or different and represent hydrogen, halogen, alkyl, alkoxy, halogenoalkyl or NO₂ and

Z represents halogen, --OH, --NHOH or the group --OR¹,

in which

R¹ denotes optionally substituted radicals from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aryl, aralkyl and heterocyclyl, or

Z represents the group ##STR4## in which R² and R³ are identical or different and denote hydrogen or optionally substituted radicals from the series comprising alkyl, aryl and a heterocyclic radical, or

Z represents the group --OM,

in which

M denotes ammonium or the equivalent of an alkali metal, alkaline earth metal or heavy metal cation,

have a particularly long-lasting high activity against nematodes or soil insects. The sulphenic acid amides of the general formula (I) are hereinbelow sometimes identified as "action prolongers" or "extenders".

The duration of action of the new pesticidal compositions is considerably longer than the duration of action of the active compounds. Since the sulphenic acid amides of the general formula (I) have virtually no nematicidal or soil-insecticidal activity at the concentrations employed, the occurrenceof the prolonging of the action must be regarded as decidedly unexpected and surprising.

Preferred active compounds for the new agents for combating pests are carbamates, P esters (including the ester-amides and the thiono, thiol and thionothiol derivatives) and pyrethroids which are usually employed as agents for combating soil pests (compare Chemistry of Pesticides, edited by K. H. Buchel, John Wiley & Sons, New York, 1983, Farm Chemicals Handbook, Meister Publishing Co., Wolloughby, 1983, U.S. Pat. No. 4,127,652 and European patent application No. 84 105 133.7 and corresponding U.S. Pat. application No. 06/606, 106).

The active compounds described below are preferred as the P esters, carbamates and pyrethroids:

(A) P esters of the general formula (II) ##STR5## in which Q represents oxygen or sulphur,

U, V and W are identical or different and represent oxygen or sulphur, it moreover also being possible for one of the radicals U, V and W to denote a direct bond or the --NH-- group,

R⁴ and R⁵ are identical or different and represent

sent C₁ -C₄ -alkyl (preferably C₁ -C₃ -alkyl) and

R⁶ represents C.sub. -C₅ -alkyl (preferably C₁ -C₂ -alkyl), which can be substituted by C₁ -C₄ -alkylthio (preferably C₁ -C₂ -alkylthio) and/or halogen (preferably chlorine), or represents C₂ -C₄ -alkenyl, which can be substituted by halogen (preferably chlorine) and/or halogenophenyl (preferably chlorophenyl) or represents phenyl, which can be substituted by halogen (preferably chlorine and/or bromine), C₁ -C₄ -alkyl (preferably methyl), C₁ -C₄ -alkylthio (preferably methylthio), C₁ -C₄ -alkylsulphinyl (preferably methylsulphinyl) and/or C₁ -C₄ -alkoxycarbonyl (preferably propoxycarbonyl), or represents pyridyl, which can be substituted by halogen (preferably chlorine) or represents pyrimidinyl, which can be substituted by C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl and/or phenyl, or represents the radical 5-chloro-1-(1-methylethyl)-1H-1,2,4-triazol-3-yl, or represents the group --N═CR⁷ (CN),

wherein

R⁷ denotes phenyl which is optionally substituted by halogen (preferably chlorine).

In formula II, R⁴ and R⁵ preferably represent methyl, ethyl or n- and i-propyl.

R⁶ preferably represents chloromethyl, propyl, ethylthiomethyl, ethylthioethyl, t-butylthiomethyl, 1-(2,4-dichlorophenyl)-2-chloro-ethen-1-yl, phenyl, 3-methyl-4-methylthio-phenyl, 4-methylsulphinyl-phenyl, 2-i-propoxycarbonylphenyl, 2,4-dichlorophenyl, 2,4,5-trichlorophenyl, 2,5-dichloro-4-bromophenyl, 3,5,6-trichloro-2-pyridyl, the radical --N═(CN) (phenyl) or the radical 5-chloro-1-(1-methylethyl)-1-H-1,2,4-triazol-3-yl.

The following P esters may be mentioned as examples (common name or chemical name): disulfoton, femamiphos, isofenfos, trichloronat, fensulfothion, protiofos, phoxim, chlorfenvinfos, bromophos, terbufos, chlorpyrifos, chlormephos, fenofos, isazophos, ethoprofos, phorate, 0-ethyl 0-i-propyl 0-(2-t-butyl-pyrimidin-5-yl) thionophosphate and 0,0-diethyl 0-(2-t-butyl-pyrimidin-5-yl) thionophosphate. Preferred esters which may be mentioned are: terbufos, chlorpyrifos, fenofos, isofenfos, fenaminphos, phorate, 0-ethyl 0-i-propyl 0-(2-t-butyl-pyrimidin-5-yl) thionophosphate and 0,0-diethyl 0-(2-t-butyl-pyrimidin-5-yl) thionophosphate.

(B) Carbamates of the general formula (III) ##STR6## in which R⁸ represents phenyl, which can be substituted by C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl (preferably ethylthiomethyl), C₁ -C₄ -alkyl (preferably methyl), C₁ -C₄ -alkoxy and/or C₁ -C₄ -alkylthio (preferably methylthio), or represents the radical 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, or represents the radical --N═CR⁹ R¹⁰,

in which

R⁹ denotes C₁ -C₄ -alkyl (preferably propyl), which can be substituted by C₁ -C₄ -alkylthio (preferably methylthio), or

R⁹ denotes the radical CON (C₁ -C₄ -alkyl)₂ preferably CONH(CH₃)₂) and

R¹⁰ denotes hydrogen or C₁ -C₄ -alkylthio (preferably methylthio),

R¹¹ represents C₁ -C₄ -alkyl (preferably methyl) and

R¹² denotes hydrogen or the radical --S--NR¹³ R¹⁴,

in which

R¹³ denotes C₁ -C₄ -alkyl and

R¹⁴ denotes COOC₁ -C₄ -alkyl (preferably n-butyl) or C₁ -C₄ -alkyl, which can be substituted by COOC₁ -C₄ -alkyl (preferably COOC₂ H₅),

R⁸ preferably represents 3,4,5-trimethylphenyl, 2-ethylthiomethylphenyl, 3,5dimethyl-4-methylthophenyl, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, --N°CH--C(CH₃)₂ (SCH₃), --N═C(SCH₃)(CON(CH₃)₂) or 2-i-propoxyphenyl,

R¹¹ preferably represents methyl.

R¹² preferably represents hydrogen, --S--N(CH₃)(COOC₄ H₉ n), --S--N(C₄ H₉ n)₂ or --S--N(iC₃ H₇)(CH₂ CH₂ COOC₂ H₅).

The following carbamates may be mentioned as examples (common name or chemical name): ethiofencarb, carbofuran, methiocarb, furatiocarb, carbosulfan, aminosulfuram, aldicarb, oxamyl and 3,4,5-trimethylphenyl carbamate. Carbamates which may be mentioned as preferred are: carbofuran, furatiocarb, carbosulfan, aminosulfuram and aldicarb.

(C) Pyrethroids of the general formula (IV) ##STR7## in which R¹⁵ represents the group ##STR8## in which R¹⁸ denotes halogen (preferably chlorine or bromine) or C₁ -C₄ -alkyl (preferably methyl) and

R¹⁹ denotes halogen (preferably chlorine or bromine), C₁ -C₄ -alkyl (preferably methyl) or phenyl, which can be substituted by halogen (preferably chlorine), or

R¹⁵ represents the group ##STR9## in which R²⁰ denotes phenyl, which can be substituted by halogen (preferably chlorine), C₁ -C₄ -halogenoalkyl (halogen is preferably chlorine or fluorine), C₁ -C₄ -halogenoalkoxy (halogen is preferably chlorine or fluorine) and/or C₁ -C₄ -alkoxy,

R¹⁶ represents hydrogen or cyano and

R¹⁷ represents phenyl, which can be substituted by halogen (preferably fluorine or chlorine) and/or phenoxy.

R¹⁸ and R¹⁹ in the groups R¹⁵ preferably represent chlorine, bromine or methyl, or R¹⁸ represents chlorine and R¹⁹ represents 4-chlorophenyl. R²⁰ preferably represents 4-chlorophenyl or 2-chloro-4-trifluoromethylphenyl.

R¹⁷ preferably represents pentafluorophenyl, 3-phenoxyphenyl or 4-fluoro-3-phenoxyphenyl.

Examples of pyrethroids which may be mentioned are (common name): phenothrin, permethrin, decamethrin, fenvalerat, fluvalinate, cyfluthrine and fenfluthrin.

The present invention thus relates to the new use of the sulphenic acid amides of the general formula (I) as agents for prolonging the action of nematicidal and insecticidal carbamates, P esters and pyrethroids, agents for combating pests containing at least one compound of the formula (I) and at least one nematicidal or insecticidal active compound from the series comprising the carbamates, P esters and pyrethroids, and the use of these agents for combating pests for combating soil pests, preferably nematodes and insects. For simplicity, the term insects will in each case also include the less important arthropods which occur as soil pests, for example ants, springtails, millepedes, termites, woodlice and root mites.

The present invention also relates to the new sulphenic acid amides of the general formula (I) in which X, Y¹ and Y² have the abovementioned meaning and Z represents the group --OM, M denoting ammonium or the equivalent of an alkali metal, alkaline earth metal or heavy metal cation, and to a process for the preparation of these salts.

The present invention also relates to the new sulphenic acid amides of the general formula (I) in which X, Y¹ and Y² have the abovementioned meanings and Z represents the group OR¹, in which R¹ denotes alkyl, alkenyl or alkinyl which is optionally substituted by halogen, cyano, alkylthio, alkoxy or alkoxyalkoxy, and to a process for the preparation of these compounds.

The other compounds of the general formula (I) are known or can be obtained by generally known methods (compare, for example, German patent application A-1,810,580, German patent application A-1,543,614 (corresponding to U.S. patent specification No. 3,597,480 and U.S. patent specification No. 3,723,628), German patent application No. B-1,293,754 and German patent application A-1,668,026 (corresponding to U.S. patent specification No.3,547,992), German patent application A-1,919,180 (corresponding to U.S. patent specification No. 3,636,076), German patent application No. A-2,257,345 and German patent application A-2,311,983).

The new salts (Z=OM) can be obtained by the generally customary salt formation methods from the acids (Z=--OH) by reaction with ammonia, amines or metal bases, such as hydroxides, carbonates and bicarbonates. The reaction is preferably carried out at 0 to 30° C. in aqueousalcoholic solution, it being possible to use lower alcohols, such as methanol or ethanol, as solvents.

The reactants are preferably employed in equimolar (or equivalent) amounts. Heavy metal salts can advantageously be obtained from the alkali metal salts in aqueous-alcoholic solutions (methanol or ethanol) by reaction with heavy metal salts (for example the chlorides or sulphates), in which case the heavy metal salts precipitate out of the solution as crystals and can easily be isolated.

The new compounds of the general formula (I) in which

X represents identical or different halogen atoms,

Y¹ and Y² are identical or different and represent hydrogen, halogen, alkyl, alkoxy, halogenoalkyl or NO₂ and

Z represents the group --OR¹, in which

R¹ denotes alkyl, alkenyl or alkinyl which is optionally substituted by halogen, cyano, alkoxy, alkylthio or alkoxyalkoxy,

can be obtained by a process in which the compounds of the general formula (V) ##STR10## in which X, Y¹ and Y² have the abovementioned meaning and

Hal represents halogen (preferably flourine or chlorine),

are reacted with compounds of the general formula (VI)

    R.sup.1 --OH                                               (VI)

in which

R¹ has the abovementioned meaning,

in the presence of an acid-binding agent and in the presence of a solvent.

Possible solvents here are all the inert organic solvents. These include ethers, such as diethyl ether, tetrahydrofuran and dioxane, hydrocarbons, such as benzene, and chlorohydrocarbons, such as chloroform and chlorobenzene.

A tertiary base, such as triethylamine, or inorganic bases, such as alkali metal hydroxides or carbonates, are added to the reaction mixture to bond the hydrogen halide formed during the reaction. It is also possible to use alkali metal alcoholates or phenolates directly as starting materials and to carry out the reaction according to the invention in the aqueous phase.

The reaction temperatures can be varied within a substantial range, and the reaction is in general carried out between 0° and 100° C., preferably between 20 and 60° C. The process is in general carried out with molar amounts. However, in many cases it has proved advantageous to employ a slight excess of the hydroxy compound (about 5-25% by weight).

The reaction mixture is worked up in the customary manner. The compounds according to the invention are either colorless crystals or oils, which, depending on the molecular weight, can frequently be distilled.

In the general formulae (I) and (V), X preferably denotes flourine or chlorine and X₃ preferably represents the radical CLF₂ or CL₂ F, and especially preferably CL₂ F.

Halogen in the definition of Y¹, Y² and Z denotes fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, and in the case of Y¹ and Y² particularly preferably chlorine and in the case of Z particularly preferably fluorine.

Alkyl and alkoxy in the definition of Y¹ and Y² preferably contain 1 to 4 carbon atoms, methyl, ethyl and n- and i-propyl and methoxy, ethoxy and n- and i-propoxy being mentioned as examples. Methyl and methoxy are particularly preferred.

Halogenoalkyl Y¹ and Y² preferably contains 1 to 4 carbon atoms and 1 to 5 identical or different halogen atoms (preferably fluorine and chlorine, in particular fluorine), trifluoromethyl, dichlorofluoromethyl and pentafluoroethyl being mentioned as examples.

Alkyl R¹ (general formulae I and VI) preferably contains 1 to 12, in particular 1 to 4, carbon atoms, methyl, ethyl and n- and i-propyl being mentioned as examples.

Alkenyl and alkinyl R¹ preferably contain 1 double or triple bond and preferably 3 to 4 carbon atoms, allyl and propargyl being mentioned as examples.

Cycloalkyl R¹ preferably contains 3 to 7, in particular 5 or 6, carbon atoms. Cyclopentyl and cyclohexyl may be mentioned as examples.

Aryl R¹ preferably denotes phenyl or naphthyl, in particular phenyl.

Aralkyl R¹ preferably contains 1 to 3 carbon atoms in the alkyl part and 5 or 10 carbon atoms in the aryl part, benzyl and phenethyl being mentioned as examples.

Heterocyclyl R¹ is a heterocyclic radical, the ring of which contains 1 or more, preferably 1 to 3, and in particular 1 or 2, identical or different hetero-atoms, such as oxygen, sulphur or nitrogen, and can be aromatic, unsaturated or saturated, and preferably contains 5 or 6 ring members. Examples which may be mentioned are: furyl, thienyl, tetrahydrofuryl, pyranyl, pyrrolyl, imidazolyl and pyridyl.

Alkyl R² and R³ preferably contains 1 to 6, in particular 1 to 4, carbon atoms, examples which may be mentioned being methyl, ethyl and n- and i-propyl.

Aryl R² and R³ preferably denotes phenyl.

The heterocyclic radicals R² and R³ have the meaning given for heterocyclyl R¹. In addition R² and R³ can together with the nitrogen atom to which they are attached form a 5- or 6-membered ring, which can be interrupted by a heteroatom (as nitrogen, oxygen or sulfur).

The radicals mentioned as optionally substituted in the invention of the radicals can carry one or more, preferably 1 to 3, and in particular 1 or 2, identical or different substituents. Examples of substituents which may be mentioned are: alkyl with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methyl, ethyl, n- and i-propyl and n-, i- and t-butyl; alkoxy with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methoxy, ethoxy, n- and i-propoxy and n-, i- and t-butoxy; alkylthio with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methythio, ethylthio, n-and i-propylthio and n-, i- and t-butylthio; halogenoalkyl with preferably 1 to 4, in particular 1 or 2, carbon atoms and preferably 1 to 5, in particular 1 to 3, halogen atoms, the halogen atoms being identical or different and halogen atoms being preferably fluorine, chlorine or bromine, in particular fluorine, such as trifluoromethyl or trichloromethyl; hydroxyl; halogen, preferably fluorine, chlorine, bromine and iodine, in particular chlorine and fluorine; cyano; nitro; amino; monalkyl- and dialkyl-amino with preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group, such as methylamino, methyl-ethyl-amino, n- and i-propylamino and methyl-n-butylamino; carboxyl; carbalkoxy with preferably 2 to 4, in particular 2 or 3, carbon atoms, such as carbomethoxy and carboethoxy; sulpho (--SO₃ H); alkylsulphonyl with preferably 1 to 4, in particular 1 or 2, carbon atoms, such as methylsulphonyl and ethylsulphonyl; and arylsulphonyl with preferably 6 or 10 aryl carbon atoms, such as phenylsulphonyl.

Ammonium M can represent the NH₄ ⁼ ion or the cation of a mono-, di- or tri-alkylamine with preferably 1 to 4, in particular 1 or 2, carbon atoms per alkyl group. Examples which may be mentioned are ammonium, methylammonium and trimethylammonium.

Preferred alkali metal, alkaline earth metal or or heavy metal cations M are the cations of sodium, potassium, calcium, magnesium, copper, zinc, manganese, nickel and iron, particular preferably of copper and zinc.

Sulphenic acid amides of the general formula (I) which are preferably employed according to the invention are those in which

X represents fluorine and chlorine (X₃ preferably representing CL₂ F or F₂ CL),

Y¹ represents hydrogen, halogen (preferably chlorine), C₁ -C₄ -alkyl (preferably methyl), C₁ -C₄ -alkoxy (preferably methoxy) or NO₂,

Y² represents hydrogen or halogen (preferably chlorine),

Z represents halogen (preferably fluorine), --OH --NHOH, --OR ¹ or --NR² R³,

in which

R¹ denotes C₁ -C₁₂ -alkyl (preferably C₁ -C₄ -alkyl) which is optionally substituted by halogen (preferably chlorine), C₁ -C₄ -alkoxy (preferably methoxy or ethoxy), C₁ -C₄ -alkylthio (preferably C₁ - or C₂ -alkylthio), C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxy (preferably methoxyethoxy) or CN, or

R¹ denotes C₂ -C₄ -alkenyl (preferably allyl) or C₃ -C₄ -alkinyl (preferably propargyl), or

R¹ denotes phenyl which is optionally substituted by halogen (preferably chlorine) or C₁ -C₄ -alkoxycarbonyl (preferably methoxycarbonyl), or

R¹ denotes thienyl which is optionally substituted by C₁ -C₄ -alkyl and/or C₁ -C₄ -alkoxycarbonyl, or

R² represents hydrogen and

R³ represents hydrogen or C₁ -C₄ -alkyl which is optionally substituted by halogen (preferably chlorine), C₁ -C₄ -alkoxy (preferably methoxy)

or CN, or

R¹ represents the group --OM,

in which

M denotes ammonium or one equivalent of an alkali metal (preferably sodium or potassium), an alkaline earth metal (preferably calcium or magnesium) or a heavy metal (preferably copper or zinc).

The novel sulphenic acid amides of the general formula (I) which are moreover preferred according to the invention are those in which

X represents fluorine and chlorine (X₃ preferably represent CL₂ F),

Y¹ represents hydrogen, C₁ -C₄ -alkyl (preferably methyl), C₁ -C₄ -alkoxy (preferably methoxy) or chlorine,

Y² represents hydrogen and

Z represents the group OR¹,

in which

R¹ denotes C₁ -C₁₂ -alkyl (preferably C₁ -C₄ -alkyl) which can be substituted by halogen (preferably chlorine), C₁ -C₄ -alkoxy (preferably methoxy or ethoxy), C₁ -C₄ -alkylthio (preferably methylthio or ethylthio) or C₁ -C₄ -alkoxy-C₁ -C₄ -alkoxy (preferably methoxy-C₁ -C₂ -alkoxy), or

in which

R¹ represents allyl or propargyl.

The new copper and zinc salts of the compounds of the general formula (I) are particularly preferred according to the invention, since, because of their solubilities, they can be particularly advantageously formulated.

Some examples of compounds of the general formula (I) which can be particularly advantageously employed according to the invention are listed below: ##STR11##

                                      TABLE 1                                      __________________________________________________________________________     Extender                                                                       No.  N(CF.sub.3)SCCX.sub.3                                                                   Y.sup.1                                                                             Y.sup.2                                                                            Z                                                       __________________________________________________________________________     1    4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OH                                                      2    3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   OH                                                      3    3-N(CF.sub.3)SCClF.sub.2                                                                H    H   OH                                                      4    4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   O1/2 Cu.sup.2+                                          5    4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   O1/2 Zn.sup.2+                                          6    4-N(CF.sub.3)SCCl.sub.2 F                                                               3-CH.sub.3                                                                          H   OH                                                      7    4-N(CF.sub.3)SCCl.sub.2 F                                                               3-CH.sub.3                                                                          H   OH                                                      8    3-N(CF.sub.3)SCCl.sub.2 F                                                               4-CH.sub.3                                                                          H   OH                                                      9    3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H                                                           10   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-CH.sub.3 O                                                                        H   OH                                                      11   3-N(CF.sub.3)SCCl.sub.2 F                                                               6-Cl H   OH                                                      12   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OH                                                      13   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   NHOH                                                    14   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl 5-NO.sub.2                                                                         OH                                                      15   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   OC.sub.12 H.sub.25                                      16   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H                                                                                   ##STR12##                                              17   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   F                                                       18   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   O1/2 Cu.sup.2+                                          19   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   O1/2 Zn.sup.2+                                          20   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CH.sub.2 Cl                                   21   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CCl.sub.3                                     22   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CH.sub.2 OCH.sub.3                            23   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CCH                                           24   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                     25   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CCl.sub.3                                     26   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   O(CH.sub.2).sub.11 CH.sub.3                             27   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CH.sub.2 OCH.sub.3                            28   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CHCH.sub.2                                    29   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CCH                                           30   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   NHCH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                  31   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   OCH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3         32   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   N(CH.sub.3)CH.sub.2 CH.sub.2 CN                         33   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   OCH.sub.3                                               34   3-N(CF.sub.3)SCCl.sub.2 F                                                               4-Cl H   OC.sub.3 H.sub.7 i                                      35   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H                                                                                   ##STR13##                                              36   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H                                                                                   ##STR14##                                              37   3-N(CF.sub.3)SCCl.sub.2 F                                                               H    H   "                                                       38   4-N(CF.sub.3)SCCl.sub.2 F                                                               H    H                                                                                   ##STR15##                                              39   3-N(CF.sub.3)SCCl.sub.2 F                                                               6 Cl H   O1/2 Zm.sup.2+                                          __________________________________________________________________________      Extender Nos. 2, 4, 5, 6, 13, 14, 19 and 25 are particularly preferred.  

The new mixtures of the active compounds and the extenders can be employed against a large number of nematodes and insects, typical soil pests being the focus, but it also being possible to affect all the other important arthropods which usually occur, or occur only purely accidentally at times, in the soil or close to the soil.

From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber. From the order of the Diplopoda, for example, Blaniulus guttulatus. From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec. From the order of the Symphyla, for example, Scutigerella immaculata. From the order of the Thysanura, for example, Lepisma saccharina. From the order of the Collembola, for example, Onychiurus armatus. From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis and Schistocerca gregaria. From the order of the Dermaptera, for example, Forficula auricularia. From the order of the Isoptera, for example, Reticulitermes spp.. From the order of the Anoplura, for example, Phylloxera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp. and Linognathus spp. From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp. From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci. From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and Triatoma spp. From the order of the Homoptera, for example, Aleurodes brassicae, Bamisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp. From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudopretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima and Tortrix viridana. From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis and Costelytra zealandica. From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa spp. From the order of the Diptera, for example, Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa. From the order of the Siphonaptera, for example, Xenopsylla cheopis and Ceratophyllus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans, Heterodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp. and Trichodorus spp.

The new agents for combating pests are particularly preferably employed against the abovementioned nematodes. Moreover, they are preferably employed against pests from the group of the "corn rootworms" of the genera Diabrotica, such as Diabrotica virgifera, Diabrotica balteata and Diabrotica longicornis.

The mixtures of active compounds and extenders can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, granules, natural and synthetic materials impregnated with active compound and very fine capsules in polymeric substances and in coating compositions for seed.

These formulations are produced in known manner, for example by mixing the active compounds with extenders, that is, liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is, emulsifying agents and/or dispersing agents, and/or foam-forming agents. In the case of the use of water as an extender, organic solvents can, for example, also be used as auxiliary solvents. As liquid solvents, there are suitable in the main: aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions, alcohols, such as butanol or glycol as well as their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulphoxide, as well as water.

As solid carriers there are suitable: for example ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as highly dispersed silicic acid, alumina and silicates; as solid carriers for granules there are suitable: for example crushed and fractionated natural rocks, such as calcite, marble, pumice, sepiolite, dolomite and brick gravel, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well as albumin hydrolysis products; as dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as well as natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.

Preferred formulation forms are granules, emulsifiable concentrates, suspension concentrates and waterdispersible powders.

The formulations in general contain between 0.1 and 95 percent by weight of the mixture of active compound and extender, preferably between 0.5 and 90%.

It is also possible to formulate the active compounds and extenders separately and to mix the formulated products, or to apply the formulated products separately in their formulations.

The mixtures according to the invention can be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with other active compounds, such as other insecticides, baits, sterilizing agents, acaricides, nematicides, fungicides or growth-regulating substances. The other insecticides, include, for example, phosphates, carbamates, carboxylates, chlorinated hydrocarbons, phenylureas, pyrethroids, substances produced by microorganisms, and others.

The active compounds according to the invention can furthermore be present in their commercially available formulations and in the use forms, prepared from these formulations, as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.

The mixtures are employed in a customary manner appropriate for the use forms. As already indicated above, it is also possible to use the active compounds and extenders in (optionally different) separate formulations in mixtures of the formulations or as separate formulations.

The active compound content of the use forms prepared from the commercially available formulations can vary within wide limits. The active compound concentration of the use forms can be from 0.0000001 to 95% by weight of active compound, preferably between 0.0001 and 20% by weight.

The proportions of active compound to extender in the formulations can vary within wide limits, depending on the chosen extender and the relative activity of the particular active compound used and the active compound content in the formulation, without the prolonging in action being lost. The ratios (weight ratios) of active compounds/extender are preferably between the ranges of 1:50 and 50:1, particularly preferably between 1:20 and 20:1 and very particularly preferably between 1:10 and 10:1.

The new mixtures of active compounds and extenders are preferably employed in amounts of between 0.1 and 10 kg/ha, preferably between 0.5 and 5 kg/ha, and particularly preferably between 0.8 and 2 kg/ha (based on the non-formulated substances).

The expert can easily determine the most advantageous formulations, compositions and use amounts for solving the particular problems with the aid of his expert knowledge or with the aid of simple orientating experiments.

The preparation of the new sulphenic acid amides according to the invention will be illustrated with the aid of the following examples:

(I) PREPARATION OF THE SALTS (Z DENOTES OM) EXAMPLE I/1 ##STR16##

A solution of 17 g (1/20 mole) of 4N-trifluoro-methyl-N-(dichlorofluoromethylthio)-aminobenzoic acid in 50 ml of methanol is added to a solution of 4.2 g (1/20 mole) of sodium bicarbonate in 50 ml of water. A vacuum is briefly applied to this aqueous-methanolic solution to remove the CO₂ formed, and a solution of 3.5 g (1/40 mole) of zinc chloride in 150 ml of water is then added dropwise. The zinc salt thereby precipitates immediately. The product is filtered off with suction and dried at 70°. Yield: 18 g; melting point: 252°-56° C.

The following salts are obtained in an analogous manner:

    ______________________________________                                          ##STR17##                                                                     Example                                                                               Position                                                                No.    of N(CF.sub.3)SCF.sub.2 Cl                                                                  Y.sup.1                                                                               Y.sup.2                                                                            M      M.p.(°C.)                         ______________________________________                                         I/2    4            H      H   1/2 Cu.sup.2+                                                                         260-262                                  I/3    4            H      H   1/2 Mg.sup.2+                                                                         110 (decom-                                                                    position                                 I/4    3            H          1/2 Zn.sup.2+                                                                         80                                       I/5    3            H      H   1/2 Cu.sup.2+                                                                         206                                      I/6    2            H      H   1/2 Zn.sup.2+                                                                         80                                       I/7    3            4-Cl   H   1/2 Zn.sup.2+                                                                         174-178                                  I/8    3            4-Cl   H   1/2 Cu.sup.2+                                                                         170                                      ______________________________________                                    

(II) PREPARATION OF THE ESTERS (Z DENOTES OR¹) EXAMPLE II/1 ##STR18##

1060 g (3.1 moles) of 3-N-(fluorodichloromethylthio)-N-(trifluoromethyl)-aminobenzoyl fluoride and 145 g (3.15 moles) of ethanol are dissolved in 3 liters of toluene, and 345 g (3.4 moles) of triethylamine are added at 20°-30° C., with cooling. The reaction mixture is stirred for about 1 hour, washed 3 times with 1 liters of water each time and dried over sodium sulphate and the solvent is distilled off in vacuo. The residue (1275 g) is then distilled in vacuo. 1058 g=82% of theory of boiling point .sub. 0.4mm Hg 122°-24° C. are obtained.

The compounds of the following examples are obtained in the same manner: ##STR19##

    __________________________________________________________________________     Example                                                                             Position of             B.p. (°C.) mm Hg                           No.  N(CF.sub.3)SCCl.sub.2 F                                                                R.sup.5'                                                                          R.sup.4'     (n.sup.20)                                        __________________________________________________________________________     II/2 3       H  CH.sub.3     115°/0.3                                   II/3 4       H  CH.sub.3     120°/0.3                                   II/4 2       H  CH.sub.3     120°/0.3                                   II/5 4       H  C.sub.4 H.sub.9 n                                                                           125°/0.2                                   II/6 3       H  C.sub.4 H.sub.9 n                                                                           140°/0.3                                   II/7 2       H  C.sub.4 H.sub.9 n                                                                           170°/0.3                                   II/8 2       H  CH.sub.2 CH.sub.2 Cl                                                                        125°/0.1                                   II/9 2       H  CH.sub.2 CCl.sub.3                                                                          138-40°/0.1                                II/10                                                                               2       H  C.sub.12 H.sub.25                                                                           179-80°/0.1                                II/11                                                                               2       H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                 125-130°/0.1                               II/12                                                                               2       H  CH.sub.2 CH═CH.sub.2                                                                    110-12°/0.1                                II/13                                                                               2       H  CH.sub.2 C.tbd.CH                                                                           112-15°/0.1                                II/14                                                                               2       H  CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                          145-50°/0.1                                II/15                                                                               2       H  C.sub.16 H.sub.33                                                                           215-20°/0.08                               II/16                                                                               2       H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                              160-63°/0.08                               II/17                                                                               3       H  CH.sub.2 CH.sub. 2 Cl                                                                       125-30°/0.08                               II/18                                                                               3       H  CH.sub.2 CCl.sub.3                                                                          140-45°/0.1                                II/19                                                                               3       H  C.sub.12 H.sub.25                                                                           185-90°/0.07                               II/20                                                                               3       H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                 126-30°/0.1                                II/21                                                                               3       H  CH.sub.2 CH═CH.sub.2                                                                    120-25°/0.1                                II/22                                                                               3       H  CH.sub.2 C═CH                                                                           123-27°/0.1                                II/23                                                                               3       H  CH.sub.2 CH.sub.2 SC.sub.2 H.sub.5                                                          150-53°/0.1                                II/24                                                                               3       H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                 (1.5164)                                          II/25                                                                               3       H  CH.sub.2 CH.sub.2 CH.sub.2 OCH.sub.3                                                        (1.5136)                                          II/26                                                                               3       H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                              154-60°/0.08                               II/27                                                                               4       H  CH.sub.2 CH.sub.2 Cl                                                                        130-35°/0.1                                II/28                                                                               4       H  CH.sub.2 CCl.sub.3                                                                          140-45°/0.08                               II/29                                                                               4       H  C.sub.12 H.sub.25                                                                           195°/0.08                                  II/30                                                                               4       H  CH.sub.2 CH.sub.2 OCH.sub.3                                                                 130-35°/0.1                                II/31                                                                               4       H  CH.sub.2 CH═CH.sub.2                                                                    120-25°/0.1                                II/32                                                                               4       H  CH.sub.2 C.tbd.CH                                                                           125-30°/0.1                                II/33                                                                               4       H  CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                          160-65°/0.12                               II/34                                                                               4       H  CH.sub.2 CH.sub.2 OCH.sub.2 CH.sub.2 OCH.sub.3                                              163-68°/0.08                               II/35                                                                               3       4-Cl                                                                              C.sub.2 H.sub.5                                                                             (1.5089)                                          II/36                                                                               3       4-Cl                                                                              CH.sub.3     (1.5153)                                          II/37                                                                               3       4-Cl                                                                              C.sub.3 H.sub.7 i                                                                           (1.5031)                                          II/38                                                                               3       4-Cl                                                                              C.sub.12 H.sub.25                                                                           (1.4867)                                          __________________________________________________________________________

The prolonged duration of action of the new mixtures according to the invention may be illustrated by the following examples.

In order rapidly to achieve advantageous results in the discovery and development of suitable extenders under laboratory and greenhouse conditions, model soils suitable for the investigations were developed and the tests were carried out at relatively high soil temperatures of 20°-25° C.

The active compounds employed in Examples A and B can be illustrated by the following formulae:

    ______________________________________                                         1.  Disulfoton:                                                                                 ##STR20##                                                     2.  Fensulfothion:                                                                              ##STR21##                                                     3.  Terbufos:                                                                                   ##STR22##                                                     4.  Fenophos:                                                                                   ##STR23##                                                     5.  Chlorpyrifos:                                                                               ##STR24##                                                     6.  Phorate:                                                                                    ##STR25##                                                     7.  Phoxim:                                                                                     ##STR26##                                                     8.  Carbofuran:                                                                                 ##STR27##                                                     9.  Isofenphos                                                                                  ##STR28##                                                     10. Fenamiphos                                                                                  ##STR29##                                                     ______________________________________                                    

EXAMPLE A

1. Model soil used

Composition (percent by weight):

60% of garden soil

30% of sand

10% of peat

2. Experimental procedure and results

For the investigations, in each case 4 mg of active compound by itself or a mixture of in each case 4 mg of active compound and 4 mg of the extenders listed were mixed with in each case 1 l of the model soil, so that the individual substances were in each case present in concentrations of 4 ppm. After storage of the soils thus pretreated, after 1 week 1/2 l of soil and after 4 weeks the remaining half l were infested with 20 seven day-old larvae of Diabrotica balteata. On the day of infestation pre-swollen corn seeds were placed on the bottom of each container so that, upon germination into seedlings, they served as food for the larvae.

In each case 6 days after the infestation with the test larvae, the degree of action of the active compound by itself and of the mixture of active compound and extender were determined in % by counting the dead and living larvae. The degree of action is 100% if all the test larvae have been destroyed, and is 0% if just as many test larvae survive as in the case of the untreated control.

The active compound, extender, amounts applied and results can be seen from the following tables:

EXAMPLE A1 ACTIVE COMPOUND: CARBOFURAN

    ______________________________________                                                      Extender No. 1                                                                 (see Table 1                                                                   above)      % Destruction of the                                  Active compound                                                                             Concentration                                                                              Diabrotica larvae after                               concentration in ppm                                                                        in ppm      1 week    4 weeks                                     ______________________________________                                         Carbofurant:                                                                             4      0           100     0                                                   10     0           100     0                                                   0      10           0      0                                                   0      30           0      0                                                   4      4           100     100                                       ______________________________________                                         Example A2 Active compound: isohpenphos                                                     Each of                                                                        Extenders Nos.                                                                 1-38                                                                           (see Table 1                                                                   above)      % Destruction of the                                  Active compound                                                                             Concentration                                                                              Diabrotic larvae after                                concentration in ppm                                                                        in ppm      1 week    4 weeks                                     ______________________________________                                         Isophenphos:                                                                             4      0           100     0                                                   10     0           100     0                                                   0      10           0      0                                                   4      4           100     100                                       ______________________________________                                    

The extenders by themselves had no destructive action in the concentrations used.

The foregoing experiments, which involved illustrative concentrations, show that the mixtures of active compounds and extenders exhibit high activity significantly longer than the active compounds themselves.

EXAMPLE B

1. Model soil used

Composition (percent by weight):

90% of sand soil

10% of peat

2. Experimental procedure and results

For the investigations, in each case 4 mg of active compound by itself or a mixture of in each case 4 mg of active compound and 10 mg of the extenders listed were mixed with in each case 1 l of the model soil, so that the individual substances were in each case present in concentrations of 4 or 10 ppm. After storage of the soils thus pretreated, after 1 week 1/2 l of soil and after 4 weeks the remaining half liter were infested with 10 seven day-old larvae of Diabrotica balteata. On the day of infestation pre-swollen corn seeds were placed on the bottom of each container so that, upon germination into seedlings, they served as food for the larvae.

In each case 6 days after infestation with the test larvae, the degree of action of the active compound by itself and of the mixture of active compound and extender was determined in % by counting the dead and living larvae. The degree of action is 100% if all the test larvae have been destroyed, and is 0% if just as many test larvae are still alive as in the case of the untreated control.

The active compound, extenders, amounts applied and results can be seen from the following tables:

Active compounds employed in Example B:

1. Disulfoton

2. Fensulfothion

3. Terbufos

4. Fenophos

5. Chlorpyrifos

6. Phorate

7. Phoxim

8. Carbofuran

9. Isofenphos

    ______________________________________                                                       Each of                                                                        Extenders Nos.                                                                 1-38                                                                           (compare                                                         Each of       Table 1 above)                                                                             % destruction of the                                 Active compounds 1-9,                                                                        Concentration                                                                              Diabotica larvae after                               concentration in ppm                                                                         in ppm      1 week  4 weeks                                      ______________________________________                                         4              0          100      0                                           4             10          100     100                                          ______________________________________                                    

The experiments with concentrations prepared purely as examples show that the mixtures of active compounds and extenders have a (high) action which is several times longer than that of the active compounds by themselves.

The foregoing experiments, which involved illustrative concentrations, show that the mixtures of active compounds and extenders exhibit high activity significantly longer than the active compounds themselves.

EXAMPLE C

Model soil and test procedure correspond to Example A. However, Musca domestica larvae were used as test larvae and the degree of action was determined after 2 and 6 weeks. Fenamiphos was used as active ingredient (active compound 10).

    ______________________________________                                                     Extender No.                                                                   (compare                                                           Active compound                                                                            Table 1 above)                                                                              % destruction of the                                  concentration                                                                              Concentration                                                                               Musca larvae after                                    in ppm      in ppm       2 weeks  6 weeks                                      ______________________________________                                         Active compound                                                                            0 ppm        100       0                                           10-4 ppm                                                                       Active compound                                                                            Extender No. 1                                                                              100      100                                          10-4 ppm    4 ppm                                                              ______________________________________                                    

It will be understood that the specification and examples are illustrative but not limitative of the present invention and that other embodiments within the spirit and scope of the invention will suggest themselves to those skilled in the art. 

We claim:
 1. A soil pesticide composition for soil application displaying an enhancing duration activity comprising(a) a pesticidally effective amount of a nematicide or insecticide selected from the group consisting of(i) a P-ester of the formula ##STR30## in which Q represents oxygen or sulphur,U, V, and W are identical or different and represent oxygen or sulphur, it moreover also being possible for one of the radicals U, V and W to denote a direct bond or the -NH-group, R⁴ and R⁵ are identical or different and represent C₁ -C₄ -alkyl and R⁶ represents C₁ -C₅ -alkyl, which can be substituted by C₁ -C₄ -alkylthio or halogen, C₂ -C₄ -alkenyl, which can be substituted by halogen or halogenophenyl, phenyl, which can be substituted by halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkoxycarbonyl, pyridyl, which can be substituted by halogen, pyrimidinyl, which can be substituted by C₁ -C₄ -alkyl, C₃ -C₆ -cycloalkyl or phenyl, 5-chloro-1-(1-methylethyl)-1H-1,2,4-triazol-3-yl, or --N═CR⁷ (CN), wherein R⁷ denotes phenyl which is unsubstituted or substituted by halogen, and (ii) a carbamate of the formula ##STR31## in which R⁸ represents phenyl, which can be substituted by C₁ -C₄ -alkylthio-C₁ -C₄ -alkyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, or --N═CR⁹ R¹⁰, in whichR⁹ denotes C₁ -C₄ -alkyl, which can be substituted by C₁ -C₄ -alkylthio, or CON (C₁ -C₄ -alklyl)₂, R¹⁰ denotes hydrogen or C₁ -C₄ -alkylthio, R¹¹ represents C₁ -C₄ -alkyl, and R¹² denotes hydrogen or --S--NR¹³ R¹⁴, in which R¹³ denotes C₁ -C₄ -alkyl and R¹⁴ denotes COOC₁ -C₄ -alkyl or C₁ -C₄ -alkyl, which can be substituted by COO-C₁ -C₄ -alkyl, and (b) an effective amount sufficient to increase the duration of activity of said nematicide or insecticide in the soil of a sulphenic acid amide of the formula ##STR32## in which X denotes a halogen atom which need not be identical in all three occurrences,Y¹ denotes hydrogen, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, NO₂ or halogen substituted C₁ -C₄ -alkyl, Y² denotes hydrogen or halogen, Z denotes halogen, --OH, --NHOH, OR¹, or ##STR33## R¹ denotes unsubstituted phenyl or phenyl substituted by halogen or C₁ -C₄ -alkoxycarbonyl; or unsubstituted thienyl or thienyl substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxycarbonyl, and R² and R³ each independently denotes hydrogen, unsubstituted C₁ -C₄ -alkyl or C₁ -C₄ -alkyl substituted by halogen, C₁ -C₄ -alkoxy or CN, wherein the weight ratio of nematicide or insecticide to sulphenic acid amide is between about 10:1 and 1:50.
 2. The composition of claim 1, wherein the weight ratio of nematicide or insecticide to sulphenic acid amide is between about 10:1 and 1:20.
 3. The composition of claim 2, wherein the weight ratio is between about 10:1 and 1:10.
 4. The composition of claim 3, wherein the weight ratio is between about 1:1 and 1:10.
 5. The composition of claim 1, wherein(a) the nematicide or insecticide is limited such that(i) for the P-esterR⁴ and R⁵ independently denote C₁ -C₃ -alkyl, and R⁶ denotes C₁ -C₂ -alkyl which can be substituted by C₁ -C₂ -alkylthio or chlorine, C₂ -C₄ -alkenyl which can be substituted by chlorine, or chlorophenyl, phenyl which can be substituted by bromine, chlorine, methyl, methylthio, methylsulphinyl or propoxycarbonyl, pyridyl which can be substituted by chlorine, pyrimidinyl which can be substituted by C₁ -C₄ -alkyl, C₃ -C₆ cycloalkyl or phenyl, 5-chloro-1-(1-methylethyl)1H-1,2,4-triazol-3-yl, or --N═CR⁷ (CN) wherein R⁷ denotes phenyl which may be substituted by chlorine, and (ii) for the carbamateR⁸ denotes phenyl which can be substituted by ethylthiomethyl, methyl, C₁ -C₄ -alkoxy or methylthio, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, or --N═CR⁹ R¹⁰ wherein R⁹ denotes propyl which may be substituted by methylthio or ##STR34## R¹⁰ denotes hydrogen or methylthio, R¹¹ denotes methyl, R¹² denotes hydrogen or --S--NR¹³ R¹⁴, R¹³ denotes C₁ -C₄ -alkyl and R¹⁴ denotes n-butyl or C₁ -C₄ -alkyl which can be substituted by COOC₂ H₅, and (b) the sulphenic acid amide is limited such thatX denotes F or Cl which need not be the same in all three occurrences, Y¹ denotes hydrogen, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or NO₂, Y² denotes hydrogen or halogen, Z denotes halogen, --OH, NHOH, OR¹ or ##STR35## R¹ denotes phenyl which may be substituted by halogen or C₁ -C₄ -alkoxycarbonyl or thienyl which may be substituted by C₁ -C₄ -aklyl or C₁ -C₄ -alkoxycarbonyl, R² denotes hydrogen or methyl, and R³ denotes hydrogen, C₁ -C₄ -alkyl which may be substituted by halogen, C₁ -C₄ -alkoxy or CN.
 6. The composition of claim 5, wherein the weight ratio of nematicide or insecticide to sulphenic acid amide is between 10:1 and 1:20.
 7. The composition of claim 6, wherein the weight ratio is between 10:1 and 1:10.
 8. The composition of claim 7, wherein the weight ratio is between 1:1 and 1:10.
 9. The composition of claims 1, 5, or 8, wherein(a) Z denotes --OH, NHOH, F, or OR¹, (b) R¹ denotes unsubstituted phenyl or phenyl substituted by halogen or C₁ -C₄ -alkoxycarbonyl, (c) X denotes --Cl₂ F, and (d) the N(CF₃)SX₃ group is in ring position 3 or 4 relative to the --COZ group.
 10. The composition of claim 9, wherein Z denotes OH, NHOH or F.
 11. The composition of claim 10, wherein the nematicide or insecticide is selected from the group consisting of disulfoton, fensulfothion, terbufos, fenophos, chlorpyrifos, phorate, phoxim, carbofuran, isophenphos, and fenamiphos.
 12. A soil pesticide composition displaying an enhanced period of activity compared to the pesticide alone comprising(a) a pesticidally effective amount of a nematicide or insecticide selected from the group consisting of(i) a P-ester of the formula ##STR36## in which Q denotes oxygen or sulphur,U, V and W are identical or different and represent oxygen or sulphur, it moreover also being possible for one of the radicals U, V and W to denote a direct bond or the --NH--group, R⁴ and R⁵ independently denote C₁ -C₄ -alkyl, and R⁶ denotes chloromethyl, propyl, ethylthiomethyl, ethylthioethyl, t-butylthiomethyl, 1-(2,4-dichlorophenyl)-2-chloro-ethen-1-yl, phenyl, 3-methyl-4-methylthio-phenyl, 4-methylsulphinyl-phenyl, 2-i-propoxy-carbonylphenyl, 2,4-dichlorophenyl, 2,4,5-trichlorophenyl, 2,5-dichloro-4-bromophenyl, 3,5,6-trichloro-2-pyridyl, --N═(CN) (phenyl) or 5-chloro-1-(1-methylethyl)-1-H-1,2,4-triazol-3-yl, and (ii) a carbamate of the formula ##STR37## in which R⁸ denotes 3,4,5-trimethylphenyl, 2-ethylthiomethylphenyl, 3,5-dimethyl-4-methylthiophenyl, 2,3-dihydro-2,2-dimethyl-7-benzofuranyl, --N═CH--C(CH₃)₂ (SCH₃), --N═C(SCH₃) (CON(CH₃)₂), or 2-iso-propoxyphenyl,R¹¹ denotes methyl, R¹² denotes hydrogen, --S--N(CH₃) (COOC₄ H₉ n), --S--N(C₄ H₉ n)₂, or --S--N(iC₃ H₇) (CH₂ CH₂ COOC₂ H₅) and (b) an effective amount sufficient to increase the duration of activity of said nematicide or insecticide in the soil of a sulphenic acid amide of the formula ##STR38## in which X denotes fluorine and chlorine which need not to be identical in all three occurrences,Y¹ denotes hydrogen, halogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or NO₂, Y² denotes hydrogen or halogen, Z denotes halogen, --OH, --NHOH, --OR¹, or ##STR39## R¹ denotes phenyl which may be substituted by halogen or C₁ -C₄ -alkoxycarbonyl, or thienyl which may be substituted by C₁ -C₄ -alkyl or C₁ -C₄ -alkoxycarbonyl, R² denotes hydrogen, and R³ denotes hydrogen, C₁ -C₄ -alkyl which may be substituted by halogen, C₁ -C₄ -alkoxy or CN, and the weight ratio of nematicide or insecticide to sulphenic acid amide is between 10:1 and 1:10.
 13. A method of controlling or preventing damage to growing crops by nematodes or soil insects comprising applying a pesticidally effective amount of the composition of claim 1 to the soil before or at the time of sowing the crops.
 14. The method of claim 13, wherein the composition of claim 1 is applied at a rate of between about 0.5 and 5 kg/ha.
 15. The method of claim 13, wherein the composition of claim 12 is utilized.
 16. The method of claim 13, wherein the composition of claim 9, is utilized at a rate of between about 0.5 and 5 kg/ha.
 17. The method of claim 13, wherein the composition of claim 10 is utilized at a rate of between about 0.5 and 5 kg/ha.
 18. The method of claim 13, wherein the composition of claim 11 is utilized at a rate of between about 0.5 and 5 kg/ha. 